Electron–molecule interactions have been studied for a long time. Most of these studies have in the past been limited to the gas phase. In the condensed-phase processes that have recently attracted attention from academia as well as industry, a theoretical understanding is mostly based on electron–molecule interaction data from these gas phase experiments. When transferring this knowledge to condensed-phase problems, where number densities are much higher and multi-body interactions are common, care must be taken to critically interpret data, in the light of this chemical environment. The paper presented here highlights three typical challenges, namely the shift of ionization energies, the difference in absolute cross-sections and branching ratios, and the occurrence of multi-body processes that can stabilize otherwise unstable intermediates. Examples from recent research in astrochemistry, where radiation driven chemistry is imminently important are used to illustrate these challenges.
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